Emulsifiable compositions, curable emulsions thereof and uses of such curable emulsions

Abstract

Provided is a non-aqueous, emulsifiable composition which, in its overall concept, comprises a substantially homogenous mixture of an unblocked polyisocyanate crosslinking agent and a surface active isocyanate reactive material. Also provided is a substantially homogeneous, curable, oil-in-water emulsion produced by, as well as a method of producing such by, the steps of admixing the components of the non-aqueous emulsifiable composition as described above and, thereafter, contacting such emulsifiable composition and an aqueous medium in proportions and under conditions so as to result in a substantially homogeneous, oil-in-water emulsion. Such curable emulsions find particular use in a variety of coatings applications.

We claim: 
     
       1. An oil-in-water emulsion comprising an aqueous medium having substantially homogeneously emulsified therein a non-aqueous substantially homogeneous emulsifiable composition comprising a mixture of: (1) an unblocked polyisocyanate crosslinking agent containing at least two reactive isocyanate groups, at least one of which is a non-primary isocyanate group, and which in and of itself is substantially hydrophobic and non-dispersible in water; and   (2) a surface active isocyanate reactive material.   
     
     
       2. The oil-in-water emulsion of claim 1, wherein the unblocked polyisocyanate crosslinking agent comprises a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol. 
     
     
       3. The oil-in-water emulsion of claim 2, wherein the polyol is trimethylolpropane. 
     
     
       4. The oil-in-water emulsion of claim 2, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       5. The oil-in-water emulsion of claim 3, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       6. The oil-in-water emulsion of claim 1, wherein the unblocked polyisocyanate crosslinking agent has an NCO content of at least 10 weight % (on a 100% solids basis), and an average NCO functionality of greater than two. 
     
     
       7. The oil-in-water emulsion of claim 1, wherein the surface active isocyanate reactive material contains isocyanate reactive functionality, hydrophilizing functionality and is polymeric in nature. 
     
     
       8. The oil-in-water emulsion of claim 7, wherein the isocyanate reactive functionality comprises hydroxyl groups. 
     
     
       9. The oil-in-water emulsion of claim 7, wherein the hydrophilizing functionality is selected from anion generating functionality and cation generating functionality. 
     
     
       10. The oil-in-water emulsion of claim 9, further comprising a neutralizing agent for the hydrophilizing functionality in an amount sufficient to render the surface active isocyanate reactive material water-dispersible. 
     
     
       11. The oil-in-water emulsion of claim 9, wherein the hydrophilizing functionality is amino. 
     
     
       12. The oil-in-water emulsion of claim 9, wherein the hydrophilizing functionality is carboxyl. 
     
     
       13. The oil-in-water emulsion of claim 7, wherein the surface active isocyanate reactive material possesses the following characteristics: a number averaged molecular weight of from about 1000 to about 50000,   an acid number of from about 15 to about 150 mg KOH/g resin, and   an amount of hydroxyl groups of from about 2.5 wt % to about 6 wt % (on a 100% solids basis).   
     
     
       14. The oil-in-water emulsion of claim 7, wherein the surface active isocyanate reactive material is selected from the group consisting of olefinic copolymers and polyesters. 
     
     
       15. The oil-in-water emulsion of claim 1, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.5:1 to about 2:1. 
     
     
       16. The oil-in-water emulsion of claim 1, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1. 
     
     
       17. The oil-in-water emulsion of claim 1, wherein: (1) the unblocked polyisocyanate crosslinking agent is a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol, has an NCO content of at least 10 weight % (on a 100% solids basis), and has an average NCO functionality of greater than two; and   (2) the surface active isocyanate reactive material contains hydroxyl groups, further contains anion generating functionality which is neutralized in an amount sufficient to render the surface active isocyanate reactive material water-dispersible, and is selected from the group consisting of olefinic copolymers and polyesters, the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material being present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1.     
     
     
       18. The oil-in-water emulsion of claim 17, wherein the polyol is trimethylolpropane. 
     
     
       19. The oil-in-water emulsion of claim 18, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       20. A method of producing a substantially homogenous oil-in-water emulsion comprising the steps of: (a) admixing (1) an unblocked polyisocyanate crosslinking agent containing at least two reactive isocyanate groups, at least one of which is a non-primary isocyanate group, and which in and of itself is substantially hydrophobic and non-dispersible in water, and (2) a surface active isocyanate reactive material, to produce a non-aqueous, substantially homogenous, emulsifiable composition; and thereafter   (b) contacting the emulsifiable composition and an aqueous medium in proportions and under conditions so as to result in a substantially homogenous, oil-in-water emulsion.   
     
     
       21. The method of claim 20, wherein the unblocked polyisocyanate crosslinking agent comprises a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol. 
     
     
       22. The method of claim 21, wherein the polyol is trimethylolpropane. 
     
     
       23. The method of claim 21, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       24. The method of claim 23, wherein the diisocyanate is meta-α,α,α',α -tetramethylxylylenediisocyanate. 
     
     
       25. The method of claim 20, wherein the unblocked polyisocyanate crosslinking agent has an NCO content of at least 10 weight % (on a 100% solids basis), and an average NCO functionality of greater than two. 
     
     
       26. The method of claim 20, wherein the surface active isocyanate reactive material contains isocyanate reactive functionality, hydrophilizing functionality and is polymeric in nature. 
     
     
       27. The method of claim 26, wherein the isocyanate reactive functionality comprises hydroxyl groups. 
     
     
       28. The method of claim 26, wherein the hydrophilizing functionality is selected from anion generating functionality and cation generating functionality. 
     
     
       29. The method of claim 28, wherein the emulsifiable composition further comprises a neutralizing agent for the hydrophilizing functionality in an amount sufficient to render the surface active isocyanate reactive material water-dispersible. 
     
     
       30. The method of claim 28, wherein the aqueous medium contains a neutralizing agent for the hydrophilizing functionality in an amount sufficient to render the surface active isocyanate reactive material water-dispersible. 
     
     
       31. The method of claim 26, wherein the hydrophilizing functionality is amino. 
     
     
       32. The method of claim 26, wherein the hydrophilizing functionality is carboxyl. 
     
     
       33. The method of claim 26, wherein the surface active isocyanate reactive material possesses the following characteristics: a number averaged molecular weight of from about 1000 to about 50000,   an acid number of from about 15 to about 150 mg KOH/g resin, and   an amount of hydroxyl groups of from about 2.5 wt % to about 6 wt % (on a 100% solids basis).   
     
     
       34. The method of claim 26, wherein the surface active isocyanate reactive material is selected from the group consisting of olefinic copolymers and polyesters. 
     
     
       35. The method of claim 20, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.5:1 to about 2:1. 
     
     
       36. The method of claim 20, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1. 
     
     
       37. The method of claim 20, wherein: (1) the unblocked polyisocyanate crosslinking agent is a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol, has an NCO content of at least 10 weight % (on a 100% solids basis), and has an average NCO functionality of greater than two; and   (2) the surface active isocyanate reactive material contains hydroxyl groups, further contains anion generating functionality which is neutralized in an amount sufficient to render the surface active isocyanate reactive material water-dispersible, and is selected from the group consisting of olefinic copolymers and polyesters, the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material being present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1.     
     
     
       38. The method of claim 37, wherein the polyol is trimethylolpropane. 
     
     
       39. The method of claim 38, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       40. A coating composition based on an oil-in-water emulsion comprising an aqueous medium having substantially homogeneously emulsified therein a film-forming, non-aqueous substantially homogeneous emulsifiable composition comprising, as the primary film-forming components, a mixture of: (1) an unblocked polyisocyanate crosslinking agent containing at least two reactive isocyanate groups, at least one of which is a non-primary isocyanate group, and which in and of itself is substantially hydrophobic and non-dispersible in water; and   (2) a surface active isocyanate reactive material.   
     
     
       41. The coating composition of claim 40, wherein the unblocked polyisocyanate crosslinking agent comprises a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol. 
     
     
       42. The coating composition of claim 41, wherein the polyol is trimethylolpropane. 
     
     
       43. The coating composition of claim 41, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       44. The coating composition of claim 42, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       45. The coating composition of claim 40, wherein the unblocked polyisocyanate crosslinking agent has an NCO content of at least 10 weight % (on a 100% solids basis), and an average NCO functionality of greater than two. 
     
     
       46. The coating composition of claim 40, wherein the surface active isocyanate reactive material contains isocyanate reactive functionality, hydrophilizing functionality and is polymeric in nature. 
     
     
       47. The coating composition of claim 46, wherein the isocyanate reactive functionality comprises hydroxyl groups. 
     
     
       48. The coating composition of claim 46, wherein the hydrophilizing functionality is selected from anion generating functionality and cation generating functionality. 
     
     
       49. The coating composition of claim 48, further comprising a neutralizing agent for the hydrophilizing functionality in an amount sufficient to render the surface active isocyanate reactive mater water-dispersible. 
     
     
       50. The coating composition of claim 48, wherein the hydrophilizing functionality is amino. 
     
     
       51. The coating composition of claim 48, wherein the hydrophilizing functionality is carboxyl. 
     
     
       52. The coating composition of claim 46, wherein the surface active isocyanate reactive material possesses the following characteristics: a number averaged molecular weight of from about 1000 to about 50000,   an acid number of from about 15 to about 150 mg KOH/g resin, and   an amount of hydroxyl groups of from about 2.5 wt % to about 6 wt % (on a 100% solids basis).   
     
     
       53. The coating composition of claim 46, wherein the surface active isocyanate reactive material is selected from the group consisting of olefinic copolymers and polyesters. 
     
     
       54. The coating composition of claim 40, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.5:1 to about 2:1. 
     
     
       55. The coating composition of claim 40, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1. 
     
     
       56. The coating composition of claim 40, further comprising a cure catalyst. 
     
     
       57. The coating composition of claim 40, comprising no cure catalyst. 
     
     
       58. The coating composition of claim 40, wherein: (1) the unblocked polyisocyanate crosslinking agent is a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol, has an NCO content of at least 10 weight % (on a 100% solids basis), and has an average NCO functionality of greater than two; and   (2) the surface active isocyanate reactive material contains hydroxyl groups, further contains anion generating functionality which is neutralized in an amount sufficient to render the surface active isocyanate reactive material water-dispersible, and is selected from the group consisting of olefinic copolymers and polyesters, the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material being present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1.     
     
     
       59. The coating composition of claim 58, wherein the polyol is trimethylolpropane. 
     
     
       60. The coating composition of claim 59, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       61. An ambient temperature curable, automotive refinish clearcoat based on an oil-in-water emulsion comprising an aqueous medium having substantially homogeneously emulsified therein a film-forming, non-aqueous substantially homogeneous emulsifiable composition comprising, as the primary film-forming components, a mixture of: (1) an unblocked polyisocyanate crosslinking agent containing at least two reactive isocyanate groups, at least one of which is a non-primary isocyanate group, and which in and of itself is substantially hydrophobic and non-dispersible in water; and   (2) a surface active isocyanate reactive material.   
     
     
       62. The clearcoat of claim 61, wherein the unblocked polyisocyanate crosslinking agent comprises a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol. 
     
     
       63. The clearcoat of claim 62, wherein the polyol is trimethylolpropane. 
     
     
       64. The clearcoat of claim 62, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       65. The clearcoat of claim 63, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate. 
     
     
       66. The clearcoat of claim 61, wherein the unblocked polyisocyanate crosslinking agent has an NCO content of at least 10 weight % (on a 100% solids basis), and an average NCO functionality of greater than two. 
     
     
       67. The clearcoat of claim 61, wherein the surface active isocyanate reactive material contains isocyanate reactive functionality, hydrophilizing functionality and is polymeric in nature. 
     
     
       68. The clearcoat of claim 67, wherein the isocyanate reactive functionality comprises hydroxyl groups. 
     
     
       69. The clearcoat of claim 67, wherein the hydrophilizing functionality is anion generating functionality. 
     
     
       70. The clearcoat of claim 69, further comprising a neutralizing agent for the hydrophilizing functionality in an amount sufficient to render the surface active isocyanate reactive mater water-dispersible. 
     
     
       71. The clearcoat of claim 69, wherein the hydrophilizing functionality is carboxyl. 
     
     
       72. The clearcoat of claim 67, wherein the surface active isocyanate reactive material possesses the following characteristics: a number averaged molecular weight of from about 1000 to about 50000,   an acid number of from about 15 to about 150 mg KOH/g resin, and   an amount of hydroxyl groups of from about 2.5 wt % to about 6 wt % (on a 100% solids basis).   
     
     
       73. The clearcoat of claim 67, wherein the surface active isocyanate reactive material is selected from the group consisting of olefinic copolymers and polyesters. 
     
     
       74. The clearcoat of claim 61, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.5:1 to about 2:1. 
     
     
       75. The clearcoat of claim 61, wherein the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material are present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1. 
     
     
       76. The clearcoat of claim 61, further comprising a cure catalyst. 
     
     
       77. The clearcoat of claim 61, comprising no cure catalyst. 
     
     
       78. The clearcoat of claim 61, wherein: (1) the unblocked polyisocyanate crosslinking agent is a urethane adduct of a diisocyanate containing at least one non-primary isocyanate group with a polyol, has an NCO content of at least 10 weight % (on a 100% solids basis), and has an average NCO functionality of greater than two; and   (2) the surface active isocyanate reactive material contains hydroxyl groups, further contains anion generating functionality which is neutralized in an amount sufficient to render the surface active isocyanate reactive material water-dispersible, and is selected from the group consisting of olefinic copolymers and polyesters, the unblocked polyisocyanate crosslinking agent and the surface active isocyanate reactive material being present in amounts such that isocyanate:isocyanate reactive functionality ratio is in the range of from about 0.8:1 to about 1.2:1.     
     
     
       79. The clearcoat of claim 78, wherein the polyol is trimethylolpropane. 
     
     
       80. The clearcoat of claim 79, wherein the diisocyanate is meta-α,α,α',α'-tetramethylxylylenediisocyanate.